Quaternary ammonium polymers



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, QUAIWAIYAWONTUMIOLWOI Artilllanenm 'Del mtolhdl' M'dshisnss-saad'Comp-y, cospos'atlalol'Delawale aiderableimportanceinrecentyear's.For examplenicrylonitrile polymers acquired importance for such-useswhen a suitable solvent was found. The preparationotpolymers wlu'ch havegood solubility aswell as. functional groups that contributeto'receptivity toward-dyestufisor can be would be of utility. Polymericquaternary mnmonium compositions alsohave. utility in the preparation ofionexchange which are of use for the purification or water, separationof ionic materials and in theconsmiction of fllm where layers otselected pH sensitivity are required.

This invention has as an objectthe preparation of polymersandcopolymers.Anotherobiectisaprocesstor the preparation of polymers having quaternaryammonium groups. Other objects-will appear hereinafter.

These objects are aecompliflied by theprocess ofthis invention wherein acompound having but one non-aromatic cm-bon-carbon unsaturation andthat'in a vinylidene. d0

CHs=C ,groupattachedtothecarbonyl carbon ofC00alkyleneradicaltheotherfreevalenceoi attachedtoaquaternary ammoniumispolymeriudatatemperaturewithintherange P -100 C. with theaid of, as aninitiator, a-free radical generating polymerization catalyst, preferablyin an aqueous solution. a

The following examples in which parts are by weight are illustrative ofthe invention.

EXAMPLE 1 Preparation ofacrylonitrile/p-methaeryloayethyltiimethylammonium sulfate copolymer Themethiodide (3.5 parts) obtained from the reaction of dimefliylaminoethylmethacrylate with methyl iodide was dissolved in water and treated withexcess silver sulfate solution. The precipitated-silver iodide wasfiltered oiand the aqueous solution of the quaternary sulfate 34.5 partsof acrylonitrile, 0.19 part of ammonium persulfate' and 0.38 part ofsodium bisulflte in atotalof500partsofwater. ThepH ofthesolution wuadjusted to-3".3 with sulfuric acid.

The polymerizationwasstarted at C. and allowed towarmspontaneouslyto'C.atwhichtemperamre itwas for two hours. The polymer (11.2 parts) was obainedatter filtration, washing and drying.

. t. A ua-aura. 1sss,su ia|No.sss, is m z, A film ofthepolymercast-fromdimethylformamide solutionshowedgoodzreceptivity to-acid dyes.

EXAMPLE II.

Copolymerization ofacrylonitrile withmeth'acryloxyethyltrimethylammonium methylsulfate Mixtures. of 450water, 0.24 part of thiourea. 0.65 part'ot dodecylmercaptan, 33.0 partsof acrylonitrile, 0.95- part of 30% hydrogen peroxide solution and 2.9parts and 1.47pa'rts, respectively, of p'methacryloxyethyltrimethylammonium methylsulfate, in aqueoussolutionwere allowed-to polymerize at pl-l 3.5 for 24 hours at 25' C. Polymerswere obtained in 42% yield and 59% yield, respectively, after the usualfiltration, washing and drying. F cast from dimethylformamide solutionshowed good receptivity? to acid dyes. The polymers showed inherentviscosities of 0.60 and 3100, respectively.

EXAMPLE Ill A mixture of 9.5- parts of styrene, 1.0 part ofmethacryloxyethyltrimeth'ylammonium p-tolucnesulfonate (fromfl-dimethylaminoethyl methacrylate and methyl ptoluenesulfonatc), 0.3part of a dispersing agent, parts of: water and 0.06- part ofa,a'-azodiisobutyramidine by solid which'wa's not toluene soluble,-which could be preesed'to alilmat' C., and which contained 0.26%.-

nitrogen corresponding to 6.4% by weight of" the quater narycom EXAMPLEIV A mixture of 9.5" m. of methyl acrylate, 1,

of fl-methacryloxyethyltrimethylammonium p-toluenesultonate,- 0.3"partof a dispersing agent, 100 parts of water and 0.07 part-0t,'-anodiisobutyramidine hydrochloride washeated-for four hoursat 60' C.under an atmosphere of nitrogen ina closed glass vessel. The whitegelatinous mass which resultedatter trituration with boiling carbontetrachloride gave on drying at 76" C./1 mm., 7.3 parts of white polymercontaining 0.17% N amounting to 4.1%

. by weight of'the quaternary monomer.

, EXAMPLE v A mixtureot l0 parts offi-methacryloxyethylu'imethylammonium p-toluenesulfonate, 50' parts ofwater and 0.03 part of a'amdiisobutyramidine hydrochloride washeatedunder an atmosphere of nitrogen for 20 hours at 63' C. Treatmentof'theresulting solution witha large volume of dioxane gave eight partsof a free-flowing, hygroscopic. white powder. The inherent viscosity ofa. 0.1823% solution of the polymer in water at- 25' C. was determined tobe 6.04.

The polymerizable monoethylenically unsaturated vinylidene quaternaryammonium compounds that may be polymerized and copolymerized by theprocess of this invention are compounds having but one non-aromaticcarbon-carbon unsaturation and. that in a vinylidene, CHs.=C groupdirectly attached to a polyatomic negative soup; i. e.,. an electronattractive. group (including nium sun, e. trialkylammoniumethyl.methacrylic ester salts, e. g., trimethylammoniumethyl methacrylatechloride; These quaternary ammonium monomers are generally obtained frommonoethylenically unsaturated vinylidene monomers containing a tertiaryamine group. The more useful monomers have the general formula hydrogen,methyl and butylgroups, and the amino substituents, R1, Rs, and-,Rraregenerally hydrocarbon free from non-aromatic unsaturation having a totalof 3 to 12 carbons and prefie rably of 3 to 9 carbons. Particularlyuseful are the lower (1 ,to 4 carbon) alkyls. The monovalent anion X issalt-forming and is generally halide,

e. g., chloride, sulfate, e. g., methyl sulfate anion, and sulfonate, e.g., para-toluene or cyclohexyl sulfonate amon.

The quaternary ammonium compounds are obtained by reaction of thetertiary with a hydrocarbon ester of an inorganic acid wherein thehydrocarbon radical has its free .valence stemming from aliphaticallysaturated carbon. In general it is more convenient to have the onevinylidene unsaturation in the tertiary amine and to use an alkylatingagent, e. g., an alkyl halide or sulfate as the quatemizingagent. Thehydrocarbon in the quaternizing agent is preferably lower alkyl, i. e.,an alkyl of 1 to 4 carbons. Examples of such esters are-alkyl halides,e. g., methyl iodide, butyl bromide, ethyl chloride; alkyl sulfates,.e.g., methyl sulfate; alkyl sulfonates, e. g., ethyl p-toluene sulfonate;alkyl phosphates, e. g., triethyl phosphate; alkyl phosphites, e. g.,triethyl phosphite; etc.

The polymerization and copolymerizan'ons of this invention arepreferably conducted in a hydroxylated solvent in which the monomericmaterial, catalyst and diluent are uniformly dispersed. Although wateris generally satisfactory, other hydroxyl containing solvents that areuseful are monohydric alcohols, particularly those of 1 to 4 carbons, e.g., tertiarybutanol. l

The time and temperature required for substantial amount ofpolymerization to take place are dependent upon the monomers andcatalyst employed. Suitable temperatures are of the order of -100 C. 1Times from one to twenty-four hours are customarily employed.

The polymerization catalyst employed is a free-radical type catalyst.Suitable catalysts are the peroxygen-compounds such as potassiumpersulfate or benzoyl peroxide, azo compounds having the azo, N=- -N',group acyclic joined to discrete non-aromatic carbons at least one ofwhich is a tertiary carbon in turn joined to carbon whose remainingvalences are satisfied by oxygen and/or nitrogen (as in U. S. 2,471,959)such as azodiis'obutyronitrile, combinations of thiourea with hydrogenperoxide, a bromate with a bisulfite, hydrogen peroxide with a titanoussalt, etc. Various of the latter type catalyst systems are effective inaqueous media at relatively low temperatures, e. g., 0-40 C. The amountof catalyst employed is generally small, e. g., 0.0l-5% by weight of thepolymerizable monomers.

Although homopolymers of certain of the quaternary salts may be preparedby the process of this invention, copolymers with other polymerizablevinylidene compounds possess greater utility inview of the combinationof physical properties along with the properties imparted by thequaternary compound.

The process of this invention is of advantage in that the reaction isclean and readily carried out under normal conditions of heat andpressure whereas the after-quaternization of a tertiary amino polymerdoes not result in complete quaternization.

The quaternary ammonium monomers can be polymerized alone, in admixturewith one or more other such increased dye absorption.

. corresponding to a quaternary monomers or virithoneor ylidenecompounds, i. e., those having a terminal methylene including oleflns,e. g., ethylene; acrylyl and 'methacrylyl compounds, e. g.,acrylonitrile, methyl acrylate, methacrylic esters and methacrylamide;vinyl and vinylidene halides, e. g., vinyl and vinylidene chloride;vinyl carboxylates, e. g., vinyl acetate; other vinyl derivatives suchas styrene and methyl vinyl ketone; and dienes such as chlorobutadieneand butadiene.

pound present in the" polymer is'proportional to the amount employedin'the' polymerization. The amount of quaternary employed is at least 1%and the amount present in the polymer including copolymer is at least0.1% and generally at least 1%.

The polymers of this invention have increased solubility and reactivitywith various modifiers, e. g., they; have The foregoing detaileddescription has been given for clearness of understanding only and nounnecessary limitations are to be understood therefrom. The invention isnot limited tothe exact details shown and described for obvious to thoseskilled in the art.

wherein n is'a cardinal number of 0 to 4, R1, Re, and R; are.hydrocarbon, free-from non-aromatic unsaturationandhavingstotalof3tol2carbonsandxisamonovalent salt-forming anion,.isbrought into contact with a free radical type polymerization catalyst inuniform dispersion in a hydroxylated solvent for the quaternary ammoniummonomer.

Z. A process for the preparation of polymers wherein a monomercomposition consisting of monomers having a non-aromatic'carbon-carbonunsaturation and that ethylenie at least 0.1% of which is amethacryloxyalkyltrialkylammonium salt is brought into contact with afree radical type polymerization catalyst in uniform dispersion in ahydroxylated solvent for-the quaternary ammonium monomer.

3. Process of claim 2 wherein thepolymerization is conducted in aqueousdispersion.

4. Process of claim 3 wherein the monomer composition contains at leastacrylonitrile and l-1S% of the quaternary ammonium monomer.

5. A copolymer of acrylonitrile containing at least 85% acrylonitrileunits and from 0.1 to 15% of units ammonium salt monomer having theformula wherein n is a cardinal number of 0 to 4, R1, Rs, and Rs arehydrocarbon free from non-aromatic unsaturation and having a total of 3to 12 carbons and X is an equivalent of a salt-forming onion.

6. A copolymer of acrylonitrile containing at least 85% acrylonitrileunits and from 0.1 to 15% of units of amethacrylyloxyalkyltrialkylammonium salt.

7. A copolymer of acrylonitrile containing at least 85 i6 acrylonitrileunits and from 0.1 to 15% of methacrylyloxyethyltrimethylammoniummethyls'ulfate units.

(Relerences on lollowlng page) more other polymeriiable vin- Usually theamount of the quaternary vinylidene com- References Cited in the file ofthis patent or the original patent UNITED STATES PATENTS Arnold Dec. 20,1947 Anthes Sept. 11, 1951 Ham Oct. 23, 1951 Ham Oct. 23, 1951 BarneyMay 4, 1954 OTHER REFERENCES Butler et al.: J. Am. Chem. Soc., 71,3120-3122 (1949).

Butler and Goette: J. Am. Chem. Soc., 74, pages 1939 et seq., April 20,1952 (abstract of the University of Florida M. S. thesis of Goette;thesis date December 8, 1950.

